I. Field of the Invention
Phosphorylsulfenyl halides are added to monoolefins, multiolefins, conjugated multiolefins and acetylenic compounds. 1,2-Markownikov oriented adducts are the principle products when conjugated diolefins are employed as the starting feedstock. Anti-Markownikov adducts are obtained as major products when unsymmetrical monoolefins and nonconjugated multiolefins are used as the starting material. The addition reactions are conducted at low temperatures. The materials which are obtained are of interest as pesticides and as intermediates in the synthesis of pesticides.
II. Description of the Prior Art
In accordance with Markownikov's rule, in the addition reaction of two organic molecules, the least hydrogenated carbon atom of one will combine with the most negative element of the other. Therefore, as disclosed by N. Kharasch, Sulfenium Ions and Sulfenyl Compounds, in "Organic Sulfur Compounds," Vol. 1, 1961, pp. 375-396, the reaction between an olefin and a sulfenyl chloride affords Markownikov-oriented products according to the following equation: ##STR1##
III. Summary of the Invention
It has now been discovered that phosphorylsulfenyl halides and thiophosphorylsulfenyl halides can be added to olefins and acetylenic compounds to form useful adducts. Anti-Markownikov oriented adducts are secured when the sulfenyl halide materials are added to unsymmetrical monoolefins and non-conjugated multiolefins. If, however, a conjugated diolefin is reacted with the sulfenyl halide material, a 1,2-Markownikov oriented adduct is produced. The adducts of the invention are useful as pesticides and as intermediates in the synthesis of pesticides.
Representative reactions contemplated by the instant invention proceed in the following manner: ##STR2##
Equation (I) illustrates the reaction of a phosphoryl or thiophosphorylsulfenyl halide with butadiene to secure 1,2 and 1,4-Markownikov oriented products. In reactions of this type, the 1,2-Markownikov oriented product predominates (greater than 50 mole %).
Equation (II) illustrates the reaction of an acylthiosulfenyl halide with an acetylenic compound to form an ethylenically unsaturated adduct product. Phosphoryl or thiophosphorylsulfenyl halides could be substituted for the acylthiosulfenyl halide employed in the reaction. The orientation of the product secured with the reactions based on acetylene depends upon the identity of the acetylenic compound and the type of solvent employed in the reaction. For example, when an alkyl substituted acetylenic compound is employed as a co-reactant, the products are primarily anti-Markownikov oriented. In contrast, when a phenylacetylene is employed as a co-reactant, the products are primarily 1,2-Markownikov oriented.
The sulfenyl halide materials that are employed in reactions with unsaturated organic compounds in accordance with the present invention have the following general formulae: ##STR3## wherein "x" is 0 or 1, R.sub.2 and R.sub.3 are monovalent, substituted or unsubstituted, hydrocarbyl radicals having from 1 to 30 carbon atoms, preferably (a) a C.sub.1 to C.sub.30, more preferably a C.sub.1 to C.sub.14 and most preferably a C.sub.1 to C.sub.6 alkyl radical, for example methyl, propyl, t-butyl, cyclohexyl, 4-ethyldodecyl, 3-butoxyheptyl, 4-chlorohexyl, decyl, 2-t-butyl-4-propylthio-nonyldecane, etc.; (b) C.sub.6 to C.sub.16 aryl radicals, e.g., phenyl, thiophenyl, thiazole, etc.; (c) C.sub.7 to C.sub.30, preferably C.sub.7 to C.sub.16, alkylaryl radicals, for example, tolyl, diethylphenyl, 2-ethyl-4-chlorophenyl, diethylnaphthyl, nonyl-phenyl, etc.; (d) C.sub.7 to C.sub.30, preferably C.sub.7 to C.sub.16 aralkyl radicals, for example, benzyl, phenylethyl, dibutylbenzyl, 2-ethyl-3-butoxybenzyl, etc.; and (e) their halo, particularly chloro and bromo, alkylthio-(radicals having from 1 to 10 carbon atoms), alkoxy-(radicals having from 1 to 10 carbon atoms), acyl and carboalkoxy-(radicals having from 1 to 10 carbon atoms) substituted derivatives; Y is a sulfur or oxygen atom and X is a halogen atom, e.g., chlorine and bromine atoms. Most preferably, R.sub.2 and R.sub.3 are methyl, ethyl or phenyl radicals, Y is an oxygen atom and X is a chlorine atom.
Representative examples of useful phosphorylsulfenyl halides and thiophosphorylsulfenyl halides include: O,O'-dimethylphosphorylsulfenyl chloride, O,O'-diethylthiophosphorylsulfenyl bromide, O,O'-diphenylphosphorylsulfenyl bromide, O,O'-dibenzylphosphorylsulfenyl bromide, O,O'-diphenylethylphosphorylsulfenyl chloride, O,O'-di-t-butylthiophosphorylsulfenyl bromide, diphenylphosphorylsulfenyl chloride, O-ethyl-phenylphosphorylsulfenyl chloride, didodecylphosphorylsulfenyl chloride, O-chlorophenyl-chloromethylphosphorylsulfenyl chloride, dibenzylphosphorylsulfenyl chloride, diphenylethylphosphorylsulfenyl chloride, ditolylphosphorylsulfenyl chloride, etc.
The unsaturated hydrocarbons employed to prepare the compositions of the instant invention are, in general, C.sub.2 to C.sub.50 hydrocarbons containing at least one acetylenic triple bond, C.sub.3 to C.sub.50 hydrocarbons containing at least one non-aromatic ethylenic double bond and analogs thereof. Useful acetylenic compounds include: C.sub.2 to C.sub.10, preferably C.sub.2 to C.sub.6 alkyl acetylenes, such as acetylene, methylacetylene, butyne-1, butyne-2, hexyne-1, octyne-3, etc.; phenyl acetylene; C.sub.9 to C.sub.14 aralkyl acetylene compounds, e.g. 3-phenylpropyne-1, 4-phenylbutyne-2, 3-phenylhexyne-1, etc.; and C.sub.9 to C.sub.14 alkyl substituted phenylacetylenes, such as 3-t-butylphenylacetylene, 2,4-diethylphenylacetylene, 2-methylphenylacetylene, 4-octylphenylacetylene, etc.
Preferably, the ethylenically unsaturated hydrocarbons are (a) C.sub.3 to C.sub.50, more preferably C.sub.3 to C.sub.30, and most preferably C.sub.3 to C.sub.13 acyclic unsymmetrical monoolefins, that is terminal olefins or internal olefins wherein the carbon atoms having the ethylenic site of unsaturation contain differing numbers of hydrogen atoms, for example, propylene, isobutylene, butene-1, dodecene-1, triacontene, hexene-1, 6-methylthiohexene-1, 8-carboethoxyoctene-1, 12-chlorododecene-1, etc.; (b) C.sub.4 -C.sub.14 conjugated and nonconjugated acyclic aliphatic multiolefins, preferably diolefins, e.g., 1,5-hexadiene, 1,6-octadiene, trivinylcyclohexane, butadiene, isoprene, chloroprene, cyanoprene, piperylene, fluoroprene, 2,5-dimethyl-2,4-hexadiene, dimethylbutadiene, etc.; (c) C.sub.3 -C.sub.12 unsymmetrical alicyclic aliphatic monoolefins, for example, 1-methylcyclopentene, 1-ethylcyclooctene, 1-butylcycloheptene, etc.; (d) C.sub.3 to C.sub.12 alicyclic aliphatic diolefins, such as 1-methylcyclododecadiene-1,5, cyclododecadiene-1,3, 1-ethyl-cyclooctadiene-1,4, cyclopentadiene, methylcyclopentadiene, dimethyldicyclopentadiene, etc.; (e) C.sub.9 to C.sub.16 alkenyl substituted aromatics, said alkenyl substitution preferably having the site of unsaturation located on the terminal carbon atom and having from 3 to 10 carbon atoms, such as allyl benzene, 5-phenylhexene-1, allylnaphthylene, etc.; and (f) halogen, preferably chlorine, substituted derivatives thereof. Most preferably, the unsaturated hydrocarbons are straight chain terminal monoolefins or C.sub.4 to C.sub.10 conjugated acyclic diolefins. The olefinic and acetylenic compounds may be substituted or unsubstituted; however it is generally preferred that they be unsubstituted. Conjugated acyclic dienes, such as butadiene and chloroprene, are of particular interest because new products are formed therefrom which have higher reactivity than simple dienes. The preferred olefinic feedstocks have from 3 to 6 carbon atoms.
The addition reactions occur at a temperature of from -100.degree. C. to +100.degree. C., preferably below about 0.degree. C. and the pressure of the reaction should be maintained at from 5 to 140 psia, preferably at atmospheric pressure. In the addition reaction between a sulfenyl halide and a monoolefin, the reactants should be present in a mole ratio of sulfenyl halide to unsaturate, from 5:1 to 1:10, preferably from 1.1:1 to 1:1.1. If a diolefin or multiolefin is employed, for example, a conjugated diene such as butadiene, a 3-10 fold, preferably 2-5 fold, excess of the unsaturate should be employed. In reactions involving acetylenic compounds, the molar ratio of sulfenyl halide to acetylenic compound within the reaction zone should be maintained between 50:1 to 2:1, preferably from 5:1 to 2:1. Preferably, the reactants are brought together in the liquid state.
If liquid olefinic or acetylenic unsaturates are utilized, the sulfenyl halide may be added slowly, preferably dropwise, to an excess of unsaturate to control the temperature. The reaction temperature is preferably maintained at less than 0.degree. C., for a period of from 0.1 to 5 hours. After the reaction is complete, the mixture is brought slowly to room temperature and the excess unsaturate and solvent are removed under reduced pressure. The crude product may be distilled under high vacuum and low temperatures.
Sulfenyl halides may be reacted with gaseous olefins by bubbling the gas through the sulfenyl halide. If has been discovered, however, that better yields are obtained if the sulfenyl halide is dropped slowly into a solution of the gaseous olefins in a suitable solvent such as methylene chloride, carbon tetrachloride, chloroform, ethyl ether, dimethyl sulfide, hydrocarbons or the like. The volume ratio of solvent to reactant, for reactions involving either gaseous or normally liquid unsaturates, may range from 0.5 to 20, preferably 1 to 10.
The novel compositions of this invention include the phosphoryl and thiophosphoryl adducts of open-chain conjugated dienes having the general formulae: ##STR4## wherein x, R.sub.2, R.sub.3, X are defined as above and R', R", R"', and R"" represent the residues of the starting C.sub.4 to C.sub.14 acyclic conjugated diolefin. More particularly, R', R", R"' and R"" denote either hydrogen atoms, chlorine atoms or monovalent lower alkyl radicals, the sum of the carbon atoms of all of the lower alkyl radicals not exceeding about 10 carbon atoms, preferably not exceeding about 6 atoms.
Other novel compositions include the monoadducts of phosphoryl sulfenyl halides and thiophosphorylsulfenyl halides with a monoacetylenic compounds, such monoadducts having the general formula ##STR5## wherein x, R.sub.2, R.sub.3, Y and X are as defined above and R.sub.4 and R.sub.5 are the residues of the starting acetylenic compound. Preferably, R.sub.4 and R.sub.5 are hydrogen atoms, monovalent alkyl radicals having from 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms (the sum of the carbon atoms of the R.sub.4 and R.sub.5 alkyl chains not exceeding about 8, preferably not exceeding about 4 carbon atoms), phenyl radicals, alkyl substituted phenyl radicals, and phenyl substituted alkyl radicals having from 7 to 16 carbon atoms.
Anti-Markownikov oriented adducts produced by the addition of thiophosphorylsulfenyl halides or phosphorylsulfenyl halides to terminal olefins are also included. Such adducts have the following general formula: ##STR6## wherein x, R.sub.2, R.sub.3, X and Y are as previously defined, and R.sub.6 and R.sub.7 are the residues of the starting terminal aliphatic monoolefin. Specifically, R.sub.6 is a C.sub.1 to C.sub.12 alkyl radical, a phenyl radical, or a C.sub.7 to C.sub.14 aralkyl radical, and R.sub.7 is a hydrogen radical or a hydrocarbyl radical of the type described with reference to R.sub.6.
The pesticidal compositions prepared with the compositions of the present invention can be employed either in solid or liquid form. When used in solid form they may be reduced to an impalpable powder and applied as an undiluted dust or mixed with a solid carrier such as clay, talc and bentonite, as well as other inert carriers known in the art. The pesticidal compositions can also be applied as an atomized spray or in a liquid carrier either as the solution in a solvent or as an emulsion in a nonsolvent such as water. In the diluted solid or liquid form the compositions of the instant invention can be employed in an amount of from between 0.01 and about 5 weight percent based on the inert carrier. Typical liquid solvents include such compounds as acetone, ethyl alcohol, benzene, naphtha and the like. Suitable wetting agents such as long chain alcohols, sulfonated amide and ester derivatives, sulfonated aromatic and mixed alkyl aryl derivatives, ester or fatty acids and petroleum sulfonates of C.sub.10 to C.sub.20 nonionic emulsifying agents can also be employed in preparing the pesticidal compositions. The compounds of this invention can also be admixed with carriers that are themselves pesticides .